Diazotype materials

ABSTRACT

WHEREIN R is substituted or unsubstituted alkyl, hydroxyalkyl, aryl, or aralkyl, and X is a radical of the formula   WHEREIN Z is a direct linkage, a divalent atom, or a divalent radical.   Diazotizable amines of the general formula   D R A W I N G

United States Patent [1 1 Garnish et al.

[4 1 Oct. 28, 1975 DIAZOTYPE MATERIALS [75] Inventors: Sidney GeorgeGarnish; Rafiqul Islam, both of London, England Related U.S. ApplicationData [62] Division of Ser. No. 56,732, June 20, 1970,

abandoned.

[30] Foreign Application Priority Data July 23, 1969 United Kingdom37095/69 [52] US. Cl.. 260/247.2 A; 260/268 H; 260/293.7l; 260/326.5 FL[51] Int. Cl. C07D 295/04 [58] Field of Search... 260/247.2 A, 268 H,293.71, 260/326.5 FL

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 728,663 2/1966Canada 260/326.5 FL 871,235 6/1961 United Kingdom 260/326.5 FL 1,330,7615/1963 France 210/3265 FL Primary Examiner-Lorraine A. WeinbergerAssistant ExaminerPaul J. Killos Attorney, Agent, or FirmW. C. Kehm [57]ABSTRACT Diazotizable amines of the general formula X g o, Cly- C uformula wherein Z is a direct linkage,'a divalent atom, or a divalentradical.

9 Claims, No Drawings DIAZOTYPE MATERIALS This is a division ofapplication Ser. No. 56,732, filed July 20, 1970, now abandoned.

The present invention relates to improved diazotype materials and toamines and diazonium compounds derived from such amines suitable for usein diazotype materials.

In the past, various diazonium compounds have been used to manufacturediazotype materials and it has been found that the desirable diazoniumcompounds for such applications are those which are very sensitive tothe light of mercury vapour lamps, both fluorescent and non-fluorescent.The diazonium compounds used should advantageously be thermally stableand yield dark colors with coupling components in the presence of asuitable developer e.g. an alkaline developer such as ammonia vapour.

A primary object of this invention is to make use of diazonium compoundswhich offer special advantages in respect of improved light-sensitivity,ease of manufacture, improved stability, and are of wider applicabilitycompared to diazonium compounds previously known for the presentpurpose.

According to one aspect of this invention we provide amines having thegeneral formula:

i l-CH wherein R is substituted or unsubstituted alkyl, hydroxy alkyl,aryl or aralkyl, and X is an optionally substituted radical X I 0R CH2--0 N 011 cu{ (II) in which X and R are as defined above and Y is ananion. Preferably Y is chloride, sulphate or a complex anion such aszinc chloride double salt.

This invention also provides a diazotype material comprising alight-sensitive layer containing a diazonium compound as defined above.

The use of the above-defined diazonium compounds offer advantages overthe compounds disclosed in U.S. Pat. No. 3,407,066 as follows:

1. The synthetic route for producing the present diazonium compounds isshorter and simpler. We have found that on certain occasions it isextremely difficult to isolate a diazonium salt in which a tertiarynitrogen is in ortho position to the diazonium group. However, in thecase of the present diazonium compounds, the presence of a carbonylgroup in the 5 membered heterocyclic ring makes the diazonium saltextremely easy to isolate.

2. As a consequence of the relative ease of preparation of thesecompounds, they are generally cheaper to produce commercially.

3. The light-sensitivity of these compounds is as high as for thecompounds disclosed in U.S. Pat. No. 3,407,066, but the thermalstability is greater. Diazotype papers based on the present diazoniumcompounds have a better shelf life than when the diazonium compoundsdisclosed in U.S. Pat. No. 3,407,066 are used.

4. When used with yellow, brown or red couplers the dyes formed have avery high actinic absorption in the ultra-violet range of wave-lenths;in addition, some of the dyes formed have deep dark brown colors. Thesetwo properties which are emphasized with the present diazonium compoundsare particularly suited for producing master intermediate prints ontranslucent materials such as cellulose film, polyester film,transparent paper and cloth or transparentised paper.

Some examples of diazonium compounds embodying the present invention arethose derived from the following amines:

2-( N-pyrrolid-2 -one-yl )-4-piperidino-5-methoxyaniline,

2-( N-pyrrolid-Z '-one-yl )-4-morpholino-5-methoxyaniline,

2-( N-pyrrolid-2 -one-yl )-4-pyrrolidino-5 -methoxyaniline,

2- N-pyrrolid-Z '-one-yl )-4-( N-methyl-piperazino )-5 methoxy-aniline.A method for preparing the amines (I) as defined above comprisescondensing a compound having the general formula:

with an optionally substituted amine having in the unsubstituted formthe general formula CH CH in which Z is as defined above to form acompound (V) having the general formula (III) but in which Cl isreplaced by the optionally substituted radical /Cll CH and reducing thecompound (V) to form the amine (I) as defined above.

Upon diazotising in a manner known per se the amines (I) are convertedinto the diazonium compounds (ll).

Compound (Ill) where R is CH may be obtained by nitrating2-chloro-4-(N-pyrrolid-2'one-yl)-anisole and the latter compound may beobtained by a condensation reaction between butyrolactone and2-chloro-4- amino-anisole.

The preparation of 2-(N-pyrrolid-2'-one-yl)-4-piperidino-methoxy-aniline may be carried out as follows: a mixture of2-chloro-4-amino-anisole and a few drops of concentrated sulphuric acidin excess butyrolactone is refluxed for eight hours in a round bottomflask fitted with a mechanical stirrer, an air condenser, a thermometerand a receiving flask, the rate of reflux is controlled by adjusting thebath temperature so that the thermometer gives a reading between 100C tol C and a distillate is collected in the receiving flask. After eighthours of simultaneous reflux and distillation as described above themixture is poured into water. The solid is isolated washed with waterand recrystallised from alcohol to give colorless needles of 2-chloro-4-(N-pyrrolid-2'-one-yl)-anisole, m.p. 8485C. The2-chloro-4-(N-pyrrolid-2-one-yl)-anisole is dissolved in glacial aceticacid and nitrated with a mixture of concentrated nitric acid andsulphuric acid in the usual way and the mixture is poured into water.The solid is collected, washed with water and recrystallised fromalcohol to give yellow needles of 2-(N-pyrrolid-2'-oneyl)-4-chloroS-methoxy-nitrobenzene, mp. 122C. The 2-( N-pyrrolid-Z'-one-yl)-4-chloro-5-methoxynitrobenzene is refluxed for ten hours withexcess piperidine and the mixture then poured into water. The solid isisolated, washed with water and recrystallised from alcohol to givebright yellow crystals of 2-(N- pyrrolid-Z -one-yl )-4-piperidino-5-methoxynitrobenzene, mp. 136C which on catalytic hydrogenation give2-(N-pyrrolid-2'-one-yl)-4-piperidino-5- methoxy-aniline. The amine canbe diazotised in the usual way and the diazonium compound can beisolated as complex salt of zinc chloride, tin chloride, borofluoride.

Similar condensation reactions of Z-(N-pyrrolid- 2'-one-yl)-4-chloroS-methoxy nitrobenzene (Formula 111) morpholine and pyrrolidine give thefollowing compounds respectively: 2-( N-pyrrolid-2'-one-yl) 4-morpholino 5-methoxy nitrobenzene, and 2-( N-pyrrolid-2-one-yl)4-pyrrolidino S-methoxy nitrobenzene, mp. 150C. A similar condensationreaction with N-methylpiperazine gives 2-(N-pyrrolid-2'-one-yl)-4-(N-methyl-piperazino)-5-methoxynitrobenzene, mp. 220C.

These nitro compounds can be reduced, diazotised and diazo compounds areisolated as complex salts of chloride, tin chloride, and borofluoride inthe usual manner.

The following examples illustrate the present invention and are not tobe regarded as limitative. All parts and properties referred to hereinand in the appended claims are by weight unless otherwise indicated.

EXAMPLE 1 A white base paper is coated with a sensitizing liquid havingthe following composition:

Water 100 ml. Tartaric acid 2 g. Thiou real 3 g.

5--methoxy benzene diazonium chloro zincate 1.5 g. Zinc chloride 2 g.2.7-Dihydroxy naphthalene 3.6disulphonic acid. disodium salt 1 g. Urea 3g.

The coated paper covered by a master tracing is exposed to a mercuryvapour lamp to obtain a latent image. The paper is developed by gaseousammonia to obtain a deep, bright blue image on a white background.

EXAMPLE 2 A white base paper is coated with a sensitizing liquid havingthe following composition:

Water 100 ml. Tartaric acid 2 g Thiourea 4 g. Diethylene glycol 3 ml.3:5 Dihydroxy N-2-hydroxy ethyl benzamide 1 5 g. 2-( Pyrrolid2'-one-yl)4-m0rpholin0-5- methoxy benzene diazonium chloro zincate 1.7 g.

The coated paper is exposed in the manner described in Example 1 anddeveloped by gaseous ammonia. The resultant copy showed a dense redimage on a white background.

EXAMPLE 3 On a polyethylene terephthalate film of the type marketed byI.C.I. Ltd. under the trade name Melinex is coated a layer of celluloseacetate butyrate. The film so obtained is subsequently coated with asensitizing liquid having the following composition:

Ethyl alcohol (95%) ml. Methyl ethyl ketone 20 ml. Citric acid 2 g. 4:6Dichloro-Resorcinol 2.6 g. 2-( Pyrrolid-l '-one-yl )-4-piperidino-5-methoxy-benzene diazonium fluoborate 2.6 g.

EXAMPLE 4 A white base paper is coated with a sensitizing liquid havingthe following composition:

The coated paper is exposed and developed as described in Example 1. Thecopy so obtained has a dense black image on a white background.

EXAMPLE 5 A transparent paper is coated with a sensitizing liquid havingthe following composition:

Water 80 ml. Ethanol ml. Citric Acid 2 g. Thiourea 3 g. 2-( Pyrrolid-Z-one-yl )-4-piperidino-5- methoxy-benzene diazonium chloro zincate 2.1g. 4:6 Dichloro-Resorcinol 2.5 g.

The resultant paper is exposed and developed as in Example 1. The copyso obtained exhibits a deep sepia image on a clear background. The lightabsorption of the image is such that excellent results are obtained whenthe copy is used as an intermediate master.

EXAMPLE 6 A tracing paper having a partially hydrolysed cellu loseacetate surface is coated with a sensitizing liquid of the followingcomposition:

Water 80 ml. Ethanol 20 ml. Citric acid 2 g. 2(N-Pyrrolid-2'-one-yl)4-pipcridino S-methoxy benzene diazonium chloride,

stannic chloride salt 5 g.

Water Phloroglucinol Resorcinol 4.5 g. Thiourea 4.5 g. PotassiumTetraborate 35 g. Potassium hydroxide 3.3 g. Sodium hydroxide 045 g.Sodium isopropyl naphthalene sulphonate 0.45 gv The pH of the aboveliquid is 9.7

The developed print so obtained exhibits a bright sepia image on a cleanbackground. Excellent results are obtained when the copy is used as anintermediate master.

This invention has been disclosed with respect to certain preferredembodiments, and it will be understood that modifications and variationsthereof will become obvious to persons skilled in the art and areintended to be included within the spirit and purview of thisapplication and the scope of the appended claims.

We claim:

1. Diazotizable amines of the general formula x. H /.OP CH c [A i 2 (f 1c Cl: CH

iii-l2 wherein R is alkyl, hydroxyalkyl, aryl, or aralkyl, and X is aradical selected from the group consisting of pyrrolidino. morpholino,piperidino and piperazino.

2. Amines according to claim 1 wherein X is pyrrolidino.

3. Amines according to claim 1 wherein X is morpholino.

4. Amines according to claim 1 wherein X is piperidino.

5. Amines according to claim 1 wherein X is piperazmo.

6. Amines according to claim 1 wherein R is methyl, and X ispyrrolidino.

7. Amines according to claim 1 wherein R is methyl and X is morpholino.

8. Amines according to claim 1 wherein R is methyl, and X is piperidino.

9. Amines according to claim 1 wherein R is methyl and X is piperazino.

1. DIAZOTIZABLE AMINES OF THE GENERAL FORMULA
 2. Amines according toclaim 1 wherein X is pyrrolidino.
 3. Amines according to claim 1 whereinX is morpholino.
 4. Amines according to claim 1 wherein X is piperidino.5. Amines according to claim 1 wherein X is piperazino.
 6. Aminesaccording to claim 1 wherein R is methyl, and X is pyrrolidino. 7.Amines according to claim 1 wherein R is methyl and X is morpholino. 8.Amines according to claim 1 wherein R is methyl, and X is piperidino. 9.Amines according to claim 1 wherein R is methyl and X is piperazino.